Process of preparing olefin chlorohydrins



S p M. NEUHAUS 2,566,355

PROCESS OF PREPARING OLEF'IN CHLOROHYDRINS Filed July 9, 1948 2" Sheets-Sheet 2 I la-3- WATER CHLORINE OLEF N STO RAG E TAN K v INVENTOR Max Neakaas Sept. 4, 1951 M- NEUHAUS PROCESS OF PREPARING OLEFIN CHLOROHYDRINS Filed July 9, 1948 2 Shee'ts-Sheet 1 Patented Sept. 4, 1951 PROCESS OF PREPARING OLEFIN CHLOROHYDR'INS Max Neuhaus, PleasantvilleljuN. Y.,; assignor to Jefferson Chemical Qompany, Inc., New York, N. Y., a corporation of Delaware Application July 9, 1948*SerialNo. 37,924

This invention relates to the production: of olefin 'c'hloroliyd'rins such 1 as f ethylene, propylene,

or mixtures df ethylene and propy leri' chlorohydriiis am relates more particularly" to the produc tiin=of "ethylene-=chlorohydrin;

Processes of producing ethylene chlorohydrin involving the introduction of a stream" of ethylene containing gas and chlorine into" a body of dilute adueous-hypochlorous' acid introduced as such or produced {by reaction or 'water with chlorine" are well known. In general such processes involve the introduction of a dilute stream of ethylene, e. gi onec ontaiiiing up to 3016 40 m'o'l percent. ethylene, the stream usuall'y containing a preponderatmg amount' of saturated hydrbcaibons, such as methane and ethane, int'o. the a'queous solution of hypochlorousacid and the withdrawal o'fan ethylenel'chlorohydrin solution iof about 6% by Weight-'0oncentrationiT Operating" under such conditions little difficulty isencountered' fronrthe standpoint of obtaining diiiusion of.the gaseous reactants-in the aqueous solution of hypochlorous acid and reaotioniofith'eidifiused rcactants.: Such operations; however; 'involve' certainobvious dis;- advantages-,Le.vg1; therea'ctor'mus't be designed to accommodaterthe; large volume? of inert'gas' mixed withsthe'olefin with 'consequents'(a)l= increased cost of thereactor, tb') l increasedp'owe'rconsumption for efiecting'i flow of the; reactants into and through :and withdrawal of the :reaction products irom'thehreactorpand (7c) material reduction in theicapacity-zof the reactor. i

b When it'is'. attempted to'pass a relatively concentrated ethylene gas'stream say;one containing .50-1mol percentaor. more of ethylene through a body lof' aqueous hypochlorous acid? solution or to which chlorine andewaterare supplied, after a relatively short period of time dispcrsiongand diffusion of the reactants into thesbody: of aqueous hypochlorous acid solution are impaired andsubtstantial. volumes ofg the; reactant-gases pass through the bodypof; SOIUtiQIIyWithOLlt reaction taking p1a e;rr u1t ne n'a materialreductioniin the yield of the desired ethylene ichlorohydrin.

Thesame p nomenon takes place WhBIlJCQnr' c n r d p pylene or c n n ra edmixt res of ethylene" andpropyleneare passedinto a body of I Another object ofnthis invention is j-to provide 19 Claims. (011260-634) aiprocess of producing olefin chlorohydrinwhich iscf highcapacity and efficiency,,particularly in that relatively high yields of the chlorohydrins are obtained and the chlorohydrin solutionproduced ispractically free of dichloride invariably formed as a by-product.

, Other objects and advantages of this invention willlbe apparent from the following detailed description thereof. 7 V A y t v .n

Inaccordance withthis invention chlorine and a relativelyconcentrated stream of an olefin of the" group consisting offlethylene, propylene and mixtures of ethylene and propyleneare diffused into a body of an aqueou solution of hypochlor- 011s acid to which bodywateris. continuously dichloride does not form in this zone.

Controlof the concentration of olefin dichloride in the zone in which the chlorine and, olefin are difiused may b eiiected by removing. the olefin dichloride to prevent its concentration exceeding the point where a separate liquid phase of olefin dichloride tends to form in this zone. For example, where the process is carried out by passing olefin and chlorine into a body of hypochlorous acid, scrubbing the reaction gases with water and passing the scrubber liquid from the scrubber into the body of hypochlorous acid, an inert gaslsuch as carbon dioxide, nitrogen, flue gas/natural gas, methane, ethane, or airvmayibe introduced above the liquidsurface inthereactor and passed in contact with the scrubber liquid along withthe inert and unreaoted gases leaving the reactor before the scrubber liquid is introducedinto the body of aqueous hypochlorous acid into which the chlorine and olefin gases are difr f used to remove olefin dichloridesfrom this liquid and therebyprevent the formation of a separate phase of olefin dichloride in the zone in; which the chlorine and olefin are iffused.v Alternatively, the suspension produced by scrubbing the reactant gases with water may be permit'tedllto settle t form water and olefin dichloride layers, thesupernatant Water layer passed to the reactor and the olefin dichloride layer Withdrawn.

Surprisingly, it has been found that by me.- venting the formation of a separate liquid phase otolefin dichloride in the zone nofthe body of aqueous hypochlorous acid in which chlorine and a concentrated stream of olefin containing in ex planation. the continuous introduction of chlorine, water cess of 50 mol percent., preferably in excess of 65 mol percent, ethylene, propylene, or mixtures of ethylene and propylene are diffused, the reaction between the olefin, chlorine and water takes place smoothly to produce olefin chlorohydrln in high yield. While the reason for this is not positively known, it is believed that the introduction of chlorine and a relatively concentrated olefin gas into a body of aqueous hypochlorous acid to which water is continuously added inevitably results in the formation of by-product olefin dichloride, the concentration of which soon reaches the point where it impairs the dispersion of the olefin and chlorine within the body of hypochlorous acid, causing large amounts of these gases to pass through the reaction zone in unreacted condition with consequent diminution of the yield of the desired chlorohydrins. By preventing the concentration of olefin dichloride from building up in the zone where the olefin and chlorine are diffused to the point such that a separate liquid phase of ethylene dichloride tends to form in this zone, the olefin and chlorine diffuse throughout the body of aqueous hypochlorous acid and react substantially completely to produce the desired chlorohydrin. Although there is good reason to believe the theory set forth above is correct, it is understood this invention is not to be limited by any statements of theory or ex- In operation this process involving and a relatively concentrated stream of an olefin fromthe group consisting of ethylene, propylene, or mixtures of ethylene and propylene into a body of aqueous hypochlorous acid while preventing the formation of a separate phase of olefin dichloride in the zone of the body of hypochlorous acid in which the olefin and chlorine are diffused results in continuous uninterrupted operation with high yields of olefin chlorohydrin.

The accompanying drawings forming a part of this specification show for purposes of exemplifi- -cation preferred forms of apparatus for practicing the process of this invention. In these drawmgs:

Figure 1 is a diagrammatic vertical sectional view partly in elevation showing one form of reactor and scrubber for practicing the process of this invention;

Figure 2 is a fragmentary diagrammatic vertical sectional view partly in elevation showing a modified form of reactor for practicing the process of this invention; and

Figure 3 is a diagrammatic vertical sectional 'view showing still another modified form of reactor and scrubber for practicing the process of this invention.

Referring to Figure 1 of the drawing, I indicates a'reactor which may desirably be in the form of an elongated cylindrical vessel having at its base an olefin inlet line II and a chlorine inlet line I2. These lines extend into the body I3 of aqueous hypochlorous acid maintained in this reactor. Chlorine line I2 is provided with diffusing thimbles I4 and olefin line H with diffusing thimbles I5 for diifusing the reactants through the body of liquid within the reactor. The portion of the body I3 of aqueous hypochlorous acid extending from the chlorine diffusing thimbles II to below the level of body I3 in which gas bubbles exist is the zone in which reaction of olefin and the exact extent will depend on the dimensions of the reactor used. The level of the top of the body of liquid I3 maintained in reactor I0 is indicated by reference character I6. Olefin chlorohydrin reaction product is withdrawn through a line I! leading from the base of reactor I0.

Reactor I0 is provided at its top with an exit lin'e I8 through which the reaction gases pass. Line I8 communicates with a scrubber I9 pro-'- vided with suitable packing I9; the gases rising through I9 are scrubbed with water admitted through line 20 disposed at the top of scrubber I9. The scrubbed reaction gas exits from scrubber I9 through line '2I-. .The suspension thus formed in scrubber I9 fiows downwardly into a decanter sec-'- tion 22 consisting of an outer chamber 23 pro vided with an olefin dichloride discharge line 24 and an inner pipe 25 disposed concentrically to provide an annular channel 26 communicating with a passage 21 leading into the reactor I0 at 28,

In operation olefin and chlorine are continuously introduced into the body of aqueous hypochlorous acid in reactor I0, the amount of olefin supplied being somewhat in excess, say from 5% to 30%, over the stoichiometric amount required to react with the chlorine to produce the olefin chlorohydrin. The olefin streamcontains at least 50 mol percent. olefin and preferably in excess of mol percent. Water is continuously supplied to top of scrubber I9 through line 20. The temperature of the water thus supplied may be within the range of from 32 to 200 F., preferably from about 60 to about 140 F.; the temperature of the body of solution I3 is within the range, of from 130 to 320 F., preferably from 150 to 260 F. Body of solution I3 is maintained at a temperature above 212 F. only when operating under superatmospheric pressure. Pressure conditions within the reactor I0 and scrubbing tower I9 preferably are atmospheric; when operating with the body of solution I3 at temperatures above the boiling point of water, as noted above, superatmospheric pressure conditions are employed, for example, up to 5 atmospheres. The chlorohydrln solution is withdrawn from the reactor when the concentration of chlorohydrin is from 3% to 20% by weight, preferably about 3% to 12%.

In the production of ethylene chlorohydrln the preferred conditions when operating at a. pressure up to 2 atmospheres absolute within the reactor and scrubber are as follows: temperature of scrubbing water from 60 to 130 F., maximum reaction temperature within reactor from 150 to 240 F., concentration of chlorohydrin solution within the reactor 3% to 12% by weight and ethylene concentration from to by volume. Operating at a pressure of 3 atmospheres absolute the preferred conditions are: temperature of scrubbing water from F., maximum reaction temperature within reactor from to 260 F., concentration of chlorohydrin solution within the reactor 3% to 12% by weight and ethylene concentration from 65% to 95% by volume. V

The rate of withdrawal-of the solution is correlated with the rate of addition of the chlorine, olefin and water; preferably the rates are correlated so that the chlorine, water and olefin are supplied continuously, a dilute chlorohydrln solution is withdrawn continuously and the body of aqueou 'hypochlorous acid within which the reactants are diffused is maintained at a contends a substantial distance above thimbles I4; 7 stant level and concentration. The particular rate of feed of reactants and withdrawal of reaction products will, of course, depend on the capacity and design of the reactor, etc. By withdrawing a relatively dilute solution having a concentration below preferably from about 3% to about 12% of chlorohydrin, side reactions are minimized.

Operating in accordance with the above conditions, for example, by continuously diffusing a aseous stream of ethylene containing from tion of a separate liquid phase of ethylene dichloride in the zone in which the reactants were diffused, it was found possible .to operate continuously for indeterminate long periods of time.

Without difficulty and with high yield of ethylene chlorohydrin. In the production of ethylene chlorohydrin the concentration of ethylene dichloride in the zone in which the reactants are diffused is preferably maintained at not exceeding .7% by weight.

Parts of Figure 2 like those of Figure 1 have been given the same reference characters. In the modification of Figure 2, reactor 10 has the product withdrawal line I! communicating with storage tank 29 and has a scrubbing section 30 integral therewith. Packing 3| is disposed within this scrubbing section on a perforated v.tray 32. Water line 2|] supplies water to this I packing asin the modification of Figure 1.. Dis- 1 posed in the gas. space 33 between the level 16 .of the body l3 of aqueous hypochlorous acid and the perforated tray 32 is a line 34 for introducing an inert .gas, such as carbon dioxide, nitrogen, flue gas, natural gas, methane, ethane .orair. This inert gas. flows with the unreacted ggases through the, scrubbing section 30 carry- .ing' with it olefin dichloride so that the olefin dichloride is not returned to the ,body '31)! :aqueoushypochlorous acid therebelow.

The modification of Figure 3 differs fromlthose of Figures 1 and. 2 in that flow of scrubber liquid through reactor Ill takes place cocurrently with the flow of thereactants; the scrubber liquid is notintroduoed into the top of the reactor so. that it flows downwardly countercurrent to the .linert andunreacted gases leaving the reactor as in Figure 1. Partsof Figure 3, the same asthose of Figure l, are indicated by the same reference characters. In Figure 3 the top of reactor ID is connected by a gasline .35 with the top of a decanter section 36.at the base of scrubbing tower [9. A line 31 leads from the top of decanter section :36 into the base of reactor it through which .line the supernatant aqueous phase flows into the base of the reactor, flowing, upwardly therethrouglialong with the reactants. A line 38 leads from the base of decanter section .34 for flow of olefin dichloride therethrough. An overflow line 39 leads from reactor l0 through which the olefin chlorohydrin reaction product flows to the storage tank.

In the operation of the apparatus of Figure 3,

.olefin and chlorine are continuously supplied to reactor l0 and cold water to scrubbing tower I9 through u'ne '20. The olefin and chlorin re ct in the body of aqueous hypochlorous acid in which line 39. Inert and unreacted gases leave the top of reactor I3 through line 35, pass up through scrubbing tower I9 where they are washed with the cold water introduced through 20. The suspension thus producedenters decanter 36 where it stratifies into an upper aqueous layer which is fed to base of reactor Ill through line 39 and a lower olefin dichloride layer withdrawn through line 38. By removing the olefin dichloride from theliquid fed into the base of reactor 10 the formation of a separate phase of olefin dichloride in the zone in which the olefin and chlorine are diffused is prevented.

As in the other modifications, the maximum temperature within the bodyof solution l3 in reactor H] of Figure 3 is within the range of from 130 to 320 F. and the pressure conditions within the reactor and scrubbing tower are preferably atmospheric, although superatinospheric pressure, for example, up to 5 atmospheres; may be employed.

The cocurrent method of Figure 3 results in smoother operation as compared with the countercurrent method of the other modifications in that it simplifies the maintenance of the desired liquid level in the reactor, and eliminates foaming difficulties. Further, a given reactor has been found to have a greater capacity for producing olefin chlorohydrin when operated with cocurrent flow therethrough as in Figure 3, rather tha countercurrent flow as in Figure 1.

Satisfactory materials of construction for equipment for practicing the process of this invention are glass, chemical stoneware, or phenolformaldehyde asbestos compositions sold under the trade name Haveg. The diffusion thimbles through which the chlorine and olefins are introduced into the body of hypochlorous acid may be made of fused crystalline aluminum oxide (Alundum) or an alumina silica mixture (Sillimanite) and maybe of any well known type designed to cause diffusion of the chlorine and olefin in very small bubbles, thereby minimizing gas phase reactions which result in formation of dichloride rather than the desired chlorohydrin.

The examples, data on which are given in the tables below, were carried out in a glass reactor section having a 4 inch internal diameter and approximately 10 feet long. A scrubber was mounted above this reactor to the top of which water was supplied continuously. Just below the reaction section four gas diffusion thimbles were mounted, two of which were employed for the diffusion of ethylene and the other two for the difiusionof the chlorine. In one series of runs ethylene was used containing mol percent. ethylene, the rest being chiefly methane and ethane. In another series of runs propylene was used, the concentration of which is indicated in Table II below. In commencing operation, water was introduced to fill the reactor to a height of about 4 feet above the diffusion thimbles. The ethylene and propylene were introduced at 2 to 3 pounds gauge pressure and their diffusion in the reactor increased the height of the liquid to approximately 9 feet. The reactor was operated at atmospheric pressure. The diffusion of chlorine into the liquid in the reactor resulted in an additional increase in the operating height to an average of about 9.25 feet above the diffusion -current to the exiting t himb les'. Tn l to 6 inclusive, the liquid was held at this level by withdrawing liquid from the bottom of the reactor at a rate correlated with the rate of introduction of the reactants. In run 7 propylene chlorohydrin solution was withdrawn from the top of the body of liquid in the reactor, as in Figure 3, and the level of the liquid thus maintained constant. e

In runs 1 and 2 carbon dioxide flowing at a rate of three to four cubic feet per minute was used as flushing agent to remove ethylene dichloride from the suspension produced by scrubbing the reaction gases with water. In runs 3, 4, 5, 6 and 7 the scrubber liquid was introduced into a' decanter, the olefin dichloride layer withdrawn and the aqueous layer fed to the reactor.

.In runs 1 to 6, inclusive, scrubbing liquid from which olefin dichloride has been removed flows into the top of the reactor in a direction counterinert and unreacted gases; in run 7 such liquid enters the base of the reactor and flows upwardly therethrough cocurrently with the reactant gases.

TABLE NO. I (CONTD) Temperatures, F.

Run 0.

Base of Re- Above Water to actor Thimbles Scrubber TABLE No. I (CONTD) Product Analysis from Base of Reactor (wt. per cent) Run No.

Ethylene Ethylene Free C12 H01 Chloro- Dihydrin chloride TABLE NO. I (CONTD) I Mols per 100 mols 012 Run No.

Ethylene Chlo- Ethylene Dirohydrin chloride 8 i T TABLE-NO. II

' firb y' cne chlorohydrin Chlorine V Duration Pmpyl' Pro 3 1- Chlorine Mol Per "'Run'Nb. of'Run, b gs m ene 11. 'Lb.Mols/ Cent Hrs. I tmtion Mols/hr.... hr. $5221 TABLE No. II (CONTD) g V i V flernperatures, If. I 5 RunNo.

'- Reactor Reactor Above Water to 'Top' Middle" Thimbles Scrubber "in 156 a 6 160 110 167 .1182. 186 140 172 181 183 147 No. ifrcorrrpi Product Analysis (Wt. Per Cent) Mols per 100 mols O12 32? Propyl- Propyl- Prop'yl- Propyl- Free ene ene ene ene 012 Dichlo- Chloro- Chloro- Dichloride hydrin hydrin ride countered. The runs were terminated when noted because it was found convenient to do so and not because of any operational difficulties. For comparative purposes it isnoted that operating under "substantially the same conditions, except that thescrubbing liquor was not treated to effect 'removal of olefin dichloride therefrom before return to the reactor, it was found impossible "to continue reasonably satisfactory operation of the reactor after about two hours. At the end of this" period coalescence of gas bubbles took place in thereactor and excessive amounts of unreacted gases escaped from the reactor.

It will be noted that this invention provides a process of producing olefin chlorohydrins in which a concentrated olefin stream and chlorine are difiused into a body of aqueous hypochlorous acid, which process overcomes the difficulties heretofore encountered when using a relatively concentrated olefin stream and is of high capacity and efficiency in that relatively high yields of olefin chlorohydrin result and the chlorohydrin solution removed from the reactor contains little or no by-product dichloride.

. Since certain changes may be made in carrying out the above process without departing from the scope of the invention it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

l. The process of preparing an olefin chlorohydrin from an olefin of the group consisting of ethylene, propylene and mixtures of ethylene and propylene, which comprises diffusing a stream of said olefin containing at least 50 mol percent. of said olefin and chlorine into a body consistascents .19 ing'of an aqueous solution of hypochlorous-acid and other reaction products resulting" from the reaction of chlorine and water while adding water to said body of hypochlorous acid, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to reactwith the chlorine to produce olefin chlorohydrin is introduced into said body, maintaining the concentration of olefin dichloride in the zone of said body into which said chlorine and olefin are diffused such that a separate liquid phase of olefin dichloride does not form in said zone, and withdrawing the solution of olefin chlorohydrin thus produced from said body.

2. The process of preparing ethylene chlorohydrin which comprises diffusing a stream of ethylene gas containing at least 50 mol percent. of ethylene and chlorine into a body consisting of an aqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine and water while adding water to said body of hypochlorous acid, the chlorine and ethylene being thus diffused inamounts such that not more than an excess'oi 30% of ethylene over the amount required'toreact with the chlorine to produce ethylene chlorohydrin is introduced into said body, maintaining the concentration of ethylene dichloride in the zone 'of'said body into which said chlorine'and ethylene are diffused such that'a separate liquid phase of ethylene dichloridedoes not form in said zone, and withdrawing the solution of ethylenechlorohydrin thus produced from said body.

3. The process of preparing propylene chlorohydrin which comprises diffusing a stream of propylene gas containing at least 50 mol percent. of propylene and chlorine into a body-consisting of an aqueous solution of hypochlorous acid'and other reaction products resulting from the'reaction of chlorine and water while addingwater tosaidbody of hypochlorous'acid, thechlorine and propylene being thus diffused in amounts such that not more than an'excess of 30% of propylene over the amount required to react with the chlorine to produce propylene chlorohydrin is introduced into 'said body, maintaining the concentration of propylene dichloride in the zone of said body into which said chlorine and propylene are diffused such that a separate liquid phase of propylene dichloride does not form in said zone, and Withdrawing the solution of propylene chlorohydrin thus producedfrom said body.

4. The process of preparing ethylene chlorohydrin, which comprises continuously adding water to a body consisting of an aqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine'and water at a temperature of from 130 to 320 F. and under a pressure such that said body is in the liquid phase, continuously diffusing chlorine and L a stream of ethylene containing at least 50 mol percent. ethylene into said body of hypochlorous acid while maintaining the concentration of ethylene dichloride Within the zone in said body in which the chlorine and ethylene are diffused not. exceeding about .7% by weight, the chlorine and ethylene being thus diffused in amounts such that not more than an excess of 30% of ethylene over theamount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, and continuously withdrawing the ethylene chlorohydrin thus produced from said body.

5. The processof preparing an olefin chlorohydrin from an olefin ofthe group consisting of ethylene, propylene and mixtureof ethylene and propylene, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperature of from 130 to 320 F; and under a pressure such that said body is in the liquid phase,:diffusing into said body'a stream of said olefin containing at least 50 mol percent. of said olefin; and chlorine, the chlorine and olefin being thus-diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced into said body, withdrawing from said body an olefin chlorohydrin solution containing from 3% to 20% by weight of olefin chlorohydrin, scrubbing the reaction gases leaving said body of solution with water, stratifying the scrubber liquid thus produced into an olefin dichloride layer and a aqueous layer, feeding the aqueous layer into said body of hypochlorous acid and removing the olefin dichloride layer.

6. The-process of preparing ethylene chlorohydrin, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperatureaof'from 150 to 240 F., continuously diffusing into said body chlorine and a stream of said-ethylene containing from to mol percent. of ethylene, the chlorine and ethylene being thus diffused in amounts such that not more than an excess of 30% of ethylene over the amount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, continuously withdrawing from said body of solutionan ethylene chlorohydrin solution containing from 3% to 12% by weight of ethylene chlorohydrin, continuously scrubbing the reaction gases leaving'said body of solution with water, continuously stratifying the scrubber liquid thus produced into an ethylene dichloride layer and anaqueous layer, continuously feeding the aqueous layer into said body of hypochlorous 'acidand continuously removing the ethylene dichloride, layer.

7. The process of preparing propylene chlorohydrin, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperature of from to 240 F., continuously diifusing into said body chlorine and a stream of said propylene containing from 70 to 95 mol percent. of propylene, the chlorine and propylene being thus diffused in amounts such that not more than an excess of 30% of propylene over the amount required to-react with the chlorine to produce propylene chlorohydrin is introduced into said body, continuously withdrawing from said body a propylene chlorohydrin solution con-. taining from 3% to 12% by weight of propylene chlorohydrin, continuously scrubbing the reaction gases leaving said body of solution with water,. continuously stratifying the scrubber liquid thus produced into a propylene dichloride layer and an aqueous layer, continuously feeding the .aqueous layer into said body of hypochlorous acid and continuously removing the propylene dichloride layer.

8. The process of preparing an olefin chlorohydrin from an olefin of the'group consisting of ethylene, propylene and mixtures of ethylene and propylene, which comprises diffusing a stream of chlorine gas and a stream of said olefin gas containing at least 50 mol percent. of said olefin into a body consisting of an aqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine and water, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin'is introduced into said body, scrubbing the reaction gases leaving said body of hypochlorous acid with water, contacting the scrubber liquid thus produced With an inert gas to remove olefin dichloride from said scrubber liquid, feeding the resultant scrubber liquid substantially free of olefindichloride to said body of hypochlorous acid, and removing from the said body of hypochlorous acid olefin chlorohydrin solution having a concentration of olefin chlorohydrin of from 3% to 20% by weight.

9. The process of preparing ethylene chlorohydrin, which comprises diffusing a stream of chlorineand a stream of said ethylene containing at least 50 mol percent. of ethylene into a body consisting of anaqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine and water, the chlorine and ethylene being thus diffused in amounts such that not more than an excess of 30% of ethylene over the amount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body of hypochlorous acid with'water, contacting the scrubber liquid thus produced with an inert gas to remove ethylene dichloride therefrom, feeding the resultant scrubber liquid substantially free of ethylene dichloride to said body of'hypochlorous acid, and removing from the said body of hypochlorous acid ethylene chlorohydrin solution having a concentration of ethylene chlorohydrin of from 3% to 20% by weight. I

10. The process of preparing propylene chlorohydrin, which comprises diffusing astream' of chlorine and a stream of said propylene contain ing at least 50 mol percent. of propylene into a body consisting of an aqueous solution of hypochlorous acid and other reaction products 'resulting from the reaction of chlorine and water, the chlorine and propylene being thus diffused in amounts such that not more than an excess of 30% of propylene over the amount required to react with the chlorine to produce propylene chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body of hypochlorous acid with water, contacting the scrub-' ber liquid thus produced with an inert'gas to remove propylene dichloride from saidtscrubber liquid, feeding the resultant scrubber liquid substantially free of propylene dichloride to said body of hypochlorous acid, and removing from the said body of hypochlorous acid propylene chlorohydrin solution having a concentration of propylene chlorohydrin of from 3% to 20% by weight; I

11. The process of preparing an olefin chloro-' chlorine and'a stream of said olefin gas contain-' ing at least 50 mol percent. of said olefin,the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced into said body, passing the reaction 12 gases leaving said body of hypochlorous acid upwardly countercurrent to a descending stream of water, thereby scrubbing said reaction gases, stratifying the scrubber liquid thus produced into an olefin dichloride layer and an aqueous layer, removing the olefin dichloride layer, feed:

ing the aqueous layer into the top portion of the said body of hypochlorous acid, and removing from the base of said body a solution containing from 3% to 20% by weight of olefin chlorohydrin. 12. The process of preparing ethylene chlorohydrin, which comprises maintaining a body of an aqueous solution of hypochlorous acid at a,

temperature of from to 320 F., diffusing into the base portion of said body a stream of chlorine and a stream of ethylene gas containing at least 50 mol percent. of ethylene, the chlorine and ethylene being thus diffused in amounts such that not more than an excess of 30% of ethyleneover the amount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, passing thereaction gases leaving said'body of hypochlorousacid upwardly countercurrent to a descending stream of water, thereby scrubbing said gases, stratifying the scrubber liquid thus produced into an ethylene dichloridelayer and-an aqueous: layer; removing the ethylene dichloride layenfeeding the aqueous layer into the top portion of the said body of hypochlorous acid, and removing from the base of said body a solution containing from 3 to 20% by weight of ethylene chlorohydrin.

13. The process of preparing an olefin chlorohydrin from an olefin of the group consisting of ethylene, propylene and mixtures of ethylene and propylene, which comprises maintaining a body of an aqueous solution of hypochlorous acid at a temperature of from 130 to 320 F., diffusing into the base portion of said body a stream of chlorine gas and a stream of said olefin gas containing at least 50 mol percent. of said olefin, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30%, of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced'into said body, passing the reaction gases leaving said body of hypochlorous acid upwardly countercurrent to a descending stream of water, thereby scrubbing said gases, contacting the scrubber liquid thus produced with a streamof inert gas to remove olefin dichloride from said scrubber liquid, said stream of inert gas flowing cocurrently with said reaction gases and countercurrent to the descending stream of water, feeding 'the scrubber liquid leaving the zone of contact with the inert gas into the top portion of said body of hypochlorous acid, and

removing from the base of said hypochlorous acid an. olefin chlorohydrin solution containing from 3 to 20% by weight of olefin chlorohydrin.

14. The process of preparing ethylene chlorohydrin, which comprises maintaining a body of an aqueous solution of hypochlorous acid at a temperature of from to 240 F., diffusing into the base portion of said body a stream of ethylene gas containing from- 70 to 95 mol percent. of ethylene, the chlorine and ethylene being thus diffused in amounts such that not more than an excessof 30% of ethylene over the amount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, passing the reaction gases leaving said body of hypochlorous acid upwardly countercurrent to a descending stream of water, thereby scrubbing said gases, contacting the scrubber liquid thus produced with a stream of inert gas to remove ethylene dichloride from said scrubber liquid, said stream of inert gas flowing cocurrently with said reaction gases and countercurrent to the descending stream of water, feeding the scrubber liquid leaving the zone of contact with the inert gas into the top portion of said body of hypochlorous acid, and removing from the base of said hypochlorous acid an ethylene chlorohydrin solution containing from 3% to 12% by weight of ethylene chlorohydrin.

15. The process of preparing an olefin chlorohydrin from an olefin of the group consisting of ethylene, propylene and mixtures of ethylene and proplyene, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperature of from 130 to 320 F., diffusing into the base of said body a stream of said olefin containing at least 50 mol percent. of said olefin and chlorine, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body with water, stratifying the scrubber liquid thus produced into an olefin dichloride layer and an aqueous layer, feeding into the base of said body the aqueous layer and causing the aqueous layer thus introduced to flow upwardly through said body, removing the olefin dichloride layer and removing from the upper portion of said body an olefin chlorohydrin solution at a rate to maintain the level of said body substantially constant.

16. The process of preparing ethylene chlorohydrin, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperature of from 150 to 240 F., diffusing into the base of said body chlorine and a stream of ethylene containing from '70 to 95 mol percent. of ethylene, the chlorine and ethylene being thus diffused in amounts such that not more than an excess of 30% of ethylene overthe amount required to react with the chlorine to produce ethylene chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body with water at a temperature of from 60 to 130 F., stratifying the scrubbing liquid thus produced into an ethylene dichloride layer and an aqueous layer, feeding into the base of said body the aqueous layer and causing the aqueous layer thus introduced to fiow upwardly through said body, removing the ethylene dichloride layer and removing from the upper portion of said body an ethylene chlorohydrin solution con taining from 3% to 12% by weight of ethylene chlorohydrin at a rate to maintain the level of said body substantially constant.

17. The process of preparing propylene chlorohydrin, which comprises establishing a body of an aqueous solution of hypochlorous acid at a temperature of from 130 to 320 F., difiusing into the base of said body a stream of propylene containing at least 50 mol percent. of propylene and chlorine, the chlorine and propylene being thus diffused in amounts such that not more than an excess of 30% of propylene over the amount required to react with the chlorine to produce propylene chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body with water, stratifying the scrubber liquid thus produced into a propylene dichloride layer and an aqueous layer, feeding into the base of said body the aqueous layer and causing the aqueous layer thus introduced to flow upwardly through said body, removing the pi tipylene dichloride layer and removing from the upper portion of said body a propylene chlorohydrin solution containing from 3% to 20% by weight of propylene chlorohydrin at a rate to maintain the level of said body substantially constant.

18. In the process of preparing an olefin chlorohydrin from an olefin of the group consisting of ethylene, propylene, and mixtures of ethylene and propylene, which comprises diffusing a stream of said olefin containing at least 50 mol percent. of said olefin and chlorine into a body consisting essentially of an aqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine and water, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of the olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced into said body, scrubbing the reaction gases leaving said body of solution with water and feeding the scrubbing liquid to said body of solution, the improvement which comprises removing olefin dichloride from the scrubbing liquid before feeding said liquid to said body of solution, thus maintaining the concentration of olefin dichloride in the zone of said body into which said chlorine and olefin are diffused such that a separate liquid phase of olefin dichloride does not form in said zone.

19. The process of preparing an olefin chlorohydrin from an olefin of the group consisting of ethylene, propylene, and mixtures of ethylene and propylene, which comprises continuously diffusing a stream of chlorine into a body consisting of an aqueous solution of hypochlorous acid and other reaction products resulting from the reaction of chlorine and Water, said body being maintained under temperature and pressure conditions such that it is in the liquid phase, continuously adding water to said body, continuously diffusing a stream of said olefin containing at least 50 mol percent. of said olefin into said body, the chlorine and olefin being thus diffused in amounts such that not more than an excess of 30% of olefin over the amount required to react with the chlorine to produce olefin chlorohydrin is introduced into said body, continuously maintaining the concentration of olefin dichloride in the zone of said body into which said chlorine and olefin are diffused such that a separate liquid phase of olefin dichloride does not form in said zone, and removing from said body an aqueous solution of the ethylene chlorohydrin thus produced.

MAX NEUHAUS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,253,616 McElroy Jan. 15, 1918 1,295,339 McElroy Feb. 25, 1919 1,456,916 Curme et al May 29, 1923 2,007,168 Kautter July 9, 1935 2,218,981 Cohen et a1 Oct. 22, 1940 2,436,591 Morrell et a1 Feb. 24, 1948 FOREIGN PATENTS Number Country Date 377,595 Great Britain July 28, 1932 

1. THE PROCESS OF PREPARING AN OLEFIN CHLOROHYDRIN FROM AN OLEFIN OF THE GROUP CONSISTTING OF ETHYLENE, PROPYLENE AND MIXTURES OF ETHYLENE AND PROPYLENE, WHICH COMPRISES DIFFUSING A STREAM OF SAID OLEFIN CONTAINGING AT LEAST 50 MOL PERCENT. OF SAID OLEFIN AND CHLORINE INTO A BODY CONSISTING OF AN AQUEOUS SOLUTON OF HYPOCHLOROUS ACID AND OTHER REACTION PRODUCTS RESULTING FROM THE REACTION OF CHLORINE AND WATER WHILE ADDING WATER TO SAID BODY OF HYPOCHLOROUS ACID, THE CHLORINE AND OLEFIN BEING THUS DIFFUSED IN AMOUNTS 